2023
DOI: 10.1002/anie.202303939
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Cu‐Bound Formates are Main Reaction Intermediates during CO2 Hydrogenation to Methanol over Cu/ZrO2

Abstract: Cu/ZrO2 is a promising catalyst for the hydrogenation of CO2 to methanol. Reaction pathways involving formates or hydroxycarbonyls have been proposed. We show here that three different types of formates can be observed under reaction conditions at 220 °C and 3 bar, one being located on metallic Cu and two others being bound to ZrO2. The surface concentrations of formates were determined through calibration curves and their reactivity measured during chemical transient experiments. The Cu‐bound formate represen… Show more

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Cited by 32 publications
(11 citation statements)
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“…They both get stronger with increasing Zr contents for those with combined Zr and Si support. However, the adsorption of formate on Cu (HCOO−Cu, at 2840, 1644, 1307 cm −1 ) [19] with two O atoms bonded to two adjacent Cu atoms are barely seen. Bands of methoxy (CH 3 O−Si or CH 3 O−Zr at 1475 and 1458–1452 cm −1 , respectively) are identified in Cu/42Zr‐SiO 2 from Figure 4c, indicating that the hydrogenation of formate to methoxy is intensified.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…They both get stronger with increasing Zr contents for those with combined Zr and Si support. However, the adsorption of formate on Cu (HCOO−Cu, at 2840, 1644, 1307 cm −1 ) [19] with two O atoms bonded to two adjacent Cu atoms are barely seen. Bands of methoxy (CH 3 O−Si or CH 3 O−Zr at 1475 and 1458–1452 cm −1 , respectively) are identified in Cu/42Zr‐SiO 2 from Figure 4c, indicating that the hydrogenation of formate to methoxy is intensified.…”
Section: Resultsmentioning
confidence: 99%
“…It has been reported that the reacting formate (HCOO−Zr) were located on ZrO 2 nanoparticles with two O atoms bonded to two adjacent Zr atoms, [18] while Meunier et al. proposed that the adsorption of formate on Cu (HCOO−Cu) with two O atoms bonded to two Cu atoms was dominant reaction pathway [19] . Without Zr component, CO 2 hydrogenation to methanol will follow the RWGS+CO‐hydro pathway on the Cu/SiO 2 catalyst according to our previous work [20] .…”
Section: Introductionmentioning
confidence: 99%
“… , Quantitatively, the initial decay and growth rate of formate FTIR signals after each switch were estimated by the slope of the curves (tangent lines in Figure d). A similar methodology has been previously applied for Cu/ZrO 2 catalysts following a CO 2 /H 2 → H 2 switch by measuring the surface concentration of HCOO* . Here, the exchange rate in moles was obtained by assuming a formate coverage value in the range of 0.10–0.20 Cu monolayers (ML), also employed by other authors for similar catalysts .…”
Section: Resultsmentioning
confidence: 99%
“…A similar methodology has been previously applied for Cu/ZrO 2 catalysts following a CO 2 /H 2 → H 2 switch by measuring the surface concentration of HCOO*. 45 Here, the exchange rate in moles was obtained by assuming a formate coverage value in the range of 0.10−0.20 Cu monolayers (ML), also employed by other authors for similar catalysts. 46 The results are presented in Table 1.…”
Section: R-wgsr + Co Hydrogenation Mechanismmentioning
confidence: 99%
“…They both get stronger with increasing Zr contents for those with combined Zr and Si support. However, the adsorption of formate on Cu (HCOOÀ Cu, at 2840, 1644, 1307 cm À 1 ) [19] with two O atoms bonded to two adjacent Cu atoms are barely seen. Bands of methoxy (CH 3 OÀ Si or CH 3 OÀ Zr at 1475 and 1458-1452 cm À 1 , respectively) are identified in Cu/ 42Zr-SiO 2 from Figure 4c, indicating that the hydrogenation of formate to methoxy is intensified.…”
Section: Analysis Of Reaction Pathwaysmentioning
confidence: 99%